Inorganic Chemistry, Vol. 14, No. 1, 1975 1129
Structural Chemistry of Ba2S3 and BaS3 5301 1-42-4; (CK3)3N-BH3, 75-22-9.
efeaences aaed Notes (1) NSF-CNRS, U. §.-France Exchange Scholar, 1973-1974. (2) (a) P.S. Bryan and R. L. Kuczkowski, Inorg. Chem., 11,553 (1972); (b) J. R. Dung, Y. S. Li, L. A. Carreira, and J. D. Odom, J. Amer. Chem. Soc., 95, 2491 (1973). (3) R. Id.Kuczkowski and D. R. Lide, Jr., J. Chem. Phys., 46,357 (1967). (4) J. P. Pasinski and R. L. Kuczkowski, J . Chem. Phys., 54, 1903 (1971). (5) D. R. Lide, Jr., R. W. Taft, Jr., and P. Love, J . Chem. Phys., 31,561 (1959): S.Geller, ibid., 32, 1569 (1960); D. R. Lide, Jr., ibid., 32, 1570 (1960). P. S. Bryan and R. L. Kuczkowski, Inorg. Chem., 10, 200 (1971). S. H. Bauer, J . Amer. Chem. SOC.,59, 1804 (1937). H. G. Schirdewahn, Doctoral 'Thesis, University of Freiburg, 1965. J. R. Durig, Y. S. Li, and J. D.Odom, J . Mol. Struct., 16, 443 (1973). Both ref 8 and 9 report spectra for the 1OB and 1lB isotopes of the (CH3)3N-BM3,(CH3)3N*BD3,(CD3)3NaBH3, and (CD3)3N*BD3species. Reference 9 also reports on the (CH3)3N.]lBD2H and (l3CH3)(12CH3)2N-IIBH3species. L. Pierce, J. Mol. Speclrosc., 3, 575 (1969). A. B. Burg and H. I. Schlesinger, J . Amer. Chem. SOC.,59,780 (1937). Two measurements (for transitions 1 and 9 in Table I) differed by +0.64 and -0.46 MHz. Fortunately, however, this does not seem to affect markedly the calculations in ref 9, except possibly the dipole moment evaluation. W. H. Kirchhoff, J . Amer. Chem. SOC.,89, 1312 (1967). J. S. Muenter, J. Chem. Phys., 48, 4544 (1968). J. Kraitchman, Amer. J . Phys., 21, 17 (1953). fi = M M / ( M 4- AM) where AM is the change in mass upon substitution and M is the mass of the parent species. L. C. Krisher and L. Pierce, J . Chem. Phys., 32, 1619 (1960). A. P. Cox and J. M. Riveros, J . Chem. Phys., 42, 3106 (1966). L. C. Krisher and L. Pierce, J. Chem. Phys., 31, 875 (1959). M is the mass of the parent species; AM = i5N mass - 14N mass; p = M M / ( M Ann); p' = M' h M / ( M ' AM), where M' is the mass of the substituted species used in eq 1. (22) Previously? d(CN) = 1.495 A; LCNB = 110.9'. (23) J. E. Wollrab and V. W. Laurie, J . Chem. Phys., 51, 1580 (1969). (24) The value of 4.90 D in ref 8 was corrected for the newer dipole moment value of OCS in ref 15. (25) N. Noth and H. Beyer, Chem. Ber., 93, 939 (1960).
+
+
(26) C. H. Bax, A. R. Katritzky, and L. E. Sutton, J . Chem. SOC.,1258 ( 1958). (27) This conclusion seems warranted based on the reports in ref 28 and 29, assuming that irreversible decomposition of the Me3N.BH3 adduct at the temperatures employed can be neglected. (28) J. M. Miller and M. Onyszchuk, Can. J . Chem., 41, 2898 (1963). (29) W. A. G. Graham and F. G. A. Stone, J. Inorg. Nucl. Chem., 3, 164 (1956). (30) T. D. Coyle and F.G. A. Stone, Progr. Boron Chem., 8 , 83 (1964). (31) R. E. McCoy and S. H. Bauer, J . Amer. Chem. SOC.,78,2061 (1956). (32) S. R. Gunn, J . Phys. Chem., 69, 1010 (1965). (33) For original literature references, see H.D. Johnson, 11, and S. G. Shore, Fortschr. Chem. Forsch., 15, 94 (1970). (34) H. C. Brown and R. R. Holmes, J. Amer. Chem. SOC.,78,2173 (1956). (35) H. C. Brown and L. Domash, J . Amer. Chem. SOC.,78,5384 (1956). (36) The interpretation that BH3 is a better acid than BF3 toward MesN has also been drawn from studies on their nmr spectra,37,3*mass spectra,39 and dipole moments.26 However, these studies are measuring effects more related to the intrinsic properties of the complexes after formation and do not necassarily indicate which adduct is more stable to dissociation as evaluated by AHG. (37) J. M. Miller and M. Onyszchuk, Can. J . Chem., 42, 1518 (1964). (38) T. D. Coyle and F.G. A. Stone, J , Amer. Chem. SOC.,83,4138 (1961). (39) G. F. Lantier and J. M. Miller, J. Chem. SOC.A , 346 (1971). (40) F. A. Cotton and J. R. Leto, J . Chem. Phys., 30, 993 (1959). (41) B. Swanson, D. F. Shriver, and J. A. Ibers, Inorg. Chem., 8,2182 (1969). (42) S. Geller and J. L. Hoard, Acta Crystallogr., 3, 121 (1950); 4, 399 (1951). (43) J. L. Hoard, S. Geller, and T. B. Owen, Acta Cryslallogr., 4,408 (1951). (44) 2.V. Zvonkova, Kristollografiya, 1,73 (1960);Sov. Phys.-Crystallogr., 2, 403 (1957). (45) A similar viewpoint was stated recently by R. W. Rudolph and R. W. Parry, J . Amer. Chem. SOC.,89, 1621 (1967). (46) E. R. Alton, Ph.D. Thesis, University of Michigan, 1960. (47) An MO estimate of the deformation energy of BF3 gave 48 kcal.40 However, no estimate for BH3 was given. (48) P. S. Ganguli and H. A. McGee, Jr., J . Chem Phys., 50, 4658 (1969). (49) For example, the nmr experiments39$40which show small differences for the two adducts lend support for this assumption. On the other hand, some unpublished data in this laboratory seem to indicate that the B-N force constants may be different. This would not be readily reconciled with the assumption although it is possible that the force constants do not reflect similar bond energies. This point deserves further investigation.
Contribution from the Materials Science Laboratory, Department of Chemical Engineering, University of Texas a t Austin, Austin, Texas 78712
istry of the Polysulfides BaB3 and S. YAMAOKA, J. T. LEMLEY, J. M. JENKS, and €4. STEINFINK* Received July 15, 1974
AIC40475D
The crystal structures of BazS3 and Bas3 were determined from three-dimensional single-crystal X-Iay diffraction data. Ba2S3 is tetragonal, I4imd, (I = b = 6.112 (1) A, c = 15.950 ( 2 ) A, Z = 4, and BaS3 is tetragonal, P421m, a = b = 6.871 (2) A, c = 4.1681 (4) A, Z = 2. Least-squares refinement gave final R's of 0.0623 for 174 observed reflections and 0.028 for 151 observed reflections, respectively. Ba2S3 contains a sulfide ion and a S22- polysulfide ion. The S-S distance in the polysulfide ion is 2.32 (9) A. One barium ion is in the center of a distorted trigonal prism whose corners are occupied by the Sz ions. The distances between Ba2+ and the nearest sulfur of the dumbbell-shaped ions are 3.1 1 and 3.91 A with three additional S2- capping the rectangular faces at 3.15 and 3.24 A. The second barium ion has an irregular polyhedron of nine sulfur atoms around it. Three of the vertices are occupied by S2- a t 3.14 and 3.72 and six vertices are occupied by S2 ions. The nearest sulfur atoms of the polysulfide ion are at 3.21 and 3.42 8, from barium. In Bas3 the polysulfide anion is S32- with S-S = 2.074 A and the S-S-S angle is 114.8'. Barium is in 12-fold coordination with Ba-S distances varying from 3.204 to 3 541 8.
~
n t ~ ~ ~ M ~ ~ ~ ~ n During high-pressure investigations of the systems Ba-Ge-S and Ba-Mn-S we frequently observed lemon yellow crystals in the reaction products. They were birefringent and X-ray diffraction powder patterns could not be matched with known patterns. Single-crystal X-ray structural investigations were carried out to determine the stoichiometries of these phases and they proved to be Ba2S3 and BaS3. The existence of BaS3 had been report& by Miller and King1 and the powder pattern due to this phase was probably not identified in our experiments
because BaS3 was a minor constituent in a multiphase reaction product. These authors deduced an incorrect unit cell and space group from their X-ray powder diffraction data but their proposed structure is remarkably accurate. The phase Ba2S3 is new and its structure was determined in this investigation. Experimental Section A single crystal of what proved to be Ba2S3 was selected from the product resulting from a high-pressure experiment carried out in a tetrahedral press a t about 50 kbars and 800" on a mixture of 3BaS Ge 2 s . The crystal had a lemon yellow color and was ap-
+
+
130 Inorganic Chemistry, Vo2. 14, No. 1, 1975
Steinfink, e/ a / ,
Tabla: 1, Atomic Parameters for Baa§, (X IO4)
._
-lll-.l-----...-_-_ll__.__.
I _ _ -
--
Atom
x
Y
Z
B1lU
Ba(l) Ba(2)
0
0 0 0 3101 (101)
-2031 (24)b
118 (19) 321 (24) 270 (83) 162 (39)
B:,
B3,
_ I _
S(1)
w.1
0 0 0
2051 (23) 0 6426 (29)
603 (42) 74 (15) -38 (5 1 ) 1155 (311)
39 (3) 13 (1) 30 (5) 74 (18)
Coefficients in the temperature factor: exp[-(Bllh2 + R 2 : k Z+ B J 2 + 2Bl,hk + 2B13hl+ 2fs,,kOl. standard error ia terms of the last digits, as derived from the variance-covariance matrix.
Bl,
B,,
____ -lll_--.._.
0
0
0
0
0 0 0
0
0 0
- . ....... -.
B2, .__... .
0 305 ( 6 2 )
The number in paranttiescs is thb:
a Figme 1. Projecrion of the structure of Ba,S, on ( 0 1 0 ) . The large circles are S and the small. circles are Ba. The numbers denoie frdcteoxa! heights along the axis of piojection and where no number is shown the atom is in the plane of projection.
proximately 50 X 41 X 29 in size. Weissenberg and precession diagrams showed that it was tetragonal with systematic absences for hkl, h i- k 1- 1 = 2n + 1, hhl, 2h 1 = 4n -I-2, and hkO, h = 2n 1, so that the space group was uniquely determined as I41/amd. Lattice constants were determined from a least-squares refinement of precise 20 values of 11 reflections between 21 and 3 1O from a crystal mounted on a single-crystal diffractometer with the instrument set at a 1' takeoff angle and a 0.05" slit in front of the scintillation counter and using h4o radiation, XI 0.70926 A, A2 0.71354 A. The lattice constants at room temperature were a = 6.1 12 (1) w a n d c = 15.950 (2) A, pcalcd 4.13 g/cm3. The single crystal of what proved to be Bas3 was found in the reaction product of a high-pressure experiment in the system BaS iMn t- S. A lemon yellow crystal was selected and Weissenberg and precession diagrams showed that it was tetragonal with the only sy2tematic absences hOO, h = 2n -f- 1, consistent with the space groups p42irn and P4212, of which the first one turned out to be correct. A least-squares refinement of 24 20 measurements under the identical conditions as above yielded the lattice parameters a = 6.871 (2) and c -- 4.1681 (4) A. pcaicd = 3.94 g/cm3. Intensity data were collected by the stationary-crystal, stationary"counter method with the instrument set at a 5' takeoff angle and no aperture in front of the counter. The pulse height discriminator was set to accept 80% of the incident Mo M a radiation; balanced Zr-Y filters were used. For Ba2S3 21 1 independent refleclions were measured to a maximum 20 = 55'. Each reflection was count& for 40 sec and only reflections which exceeded background by 8 counts were considered observed; this criterion reduced the final number to 174. The same procedure was used to measure 163 reflections from BaS3 except that the counting interval was 20 sec and the peak count had to exceed background by 15 counts. The number of reflections exceeding background was 151. Both sets of intensity data were corrected in the usual manner for Lorentz, polarization, and absorption to obtain the structure factors. Standard deviations werc assigned using the formula
-+
+
where K is the product of all correction factors and ZY and Izr are the counts with the respective filters in the diffracted beam path. Although the atomic compositions and stoichiometries of the crystals were unknown, the structures were easily solved from the three-dimensional. Patterson function. In the case of Ba2S3 some
difficulties were initially encountered. The interpretation of' the Patterson function required the location of a S atom in position 16(b) of I4ilamd and this led to an unreasonably short S-S distance in the, symmetry related atoms. The removal of the center of symmetry and considerations based on the construction of various models showcd that I4imd was the correct space group. Xt can be seen from 7 ablc I that Ba(l), Ba(2), and S( 1) atomic positions arc centrically reiateii and only S ( 2 ) positions destroy the center, The location of r.liree oC the four atoms in the asymmetric unit in special position 4(a) olNii.n/X means that hkO reflections are observed only fa.h =I 2ii so that 14i/amd is sirnuiated by the, diffmcrion data A least-squares refinement usiag anisotropic temper converged to K = 0.0623 and RIv = 0.04.73 for the ~ I itw = [e structure factors ( R =: Z ~ ~ -FiFcil/ZlfiaI, 2wF021iP).Scattering factors Poi Ba, W ,and S;-, for sulfar in 8(bj, were used2 and, after the stoichiornetry was known, the absorption correction was calculated by approximating the crystal shape with 11 faces. The final atomic paraiiieters are listed in Table 1 and the observed and calculated structurc factors are listed in Table 11. The rather large standard deviations of the parameters are due to the small size of the crystal and the resultant low intensities of thc reflections. A final difference Fourier map showed no p e a k greater than 1 e hh-3, The least-squares refinement of the observed 151 BaS3 structurr: factors converged to X -- 0.026 and Rvi = 0.032. The structure facton are listed in Table TI1 and the atomic parameters in Table I V . Scattering factors for Baz+ and S- were used in the calculatiort. Uic final difference Fourier map did not have any peaks exceeding I c 11-3. The programs used in the structure determination and their. authors were as follows: ORFIS. W. R. Busing and H.A. Levy; I N C O ~ , R. E. Davis; DAESD, D. R. Harris; RFOIJR. S . T. Wao; XRI~SPX: ?. 1, Shapiro; LSLAT: K. Y. Trueblood; ORABS, J. Williams. ~~~~U~~~~~~
Projections of the s t r u c t u r e s a r e sho:p,im in b'igures 1 arid 2 a n d i n t e r a t o m i c distances are SIIQVW in 'I'akkc!; 'V a1148 VI. Two different types of s u l f ~ are r present in B~21S3,SZ-, a n d S21--, with the former in the 4 ( a ) a n d the latter in t h positions of t h e space group. $(I) is surrounded by three a n d three Ba(2) atoms at distances of 3.14-3.27 essentially the sum of t h e ionic radii; the S(2) atoms are 2.32 88 a p a r t . It should be noted that the vibration ellipsoid of S(2) is strongly elongated a l o n g the S--S bond direction, Ba(1) is in the c e n t e r of a distorted trigonal p r i s m whose corners a r e occupied by six S 2 ions a n d the t h r e e rectangular faces are c a p p e d by t h r e e S ions. The prisms form infinite
A,
Structural Chemistry of Ba2S3 and Bas3
Inorganic Chemistry, Vol. 14, No. I , 1975 131
Table J Y. Atomic Parameters for Bas, (X l o 4 ) Atom Ba S(1) S(2)
X
Y
B1lU
Z
Bzz
B,Z
B33
B,,
BI,
0 44 (4)b 44 186 (7) 0 0 0 38 (14) 1(16) 0 0 2060 (15) 38 141 (32) 6797 28 (9) 28 235 (28) -13 (7) -2 (30) 2 4760 (17) a Coefficients in the temperature factor: expJ-(B,,h2 iB2,kZ + B,,EZ + 2B,,hk + 2Bl,hI + 2B2,kl)]. Symmetry-related values are indicated by the omission of the standard deviations. b The number in parentheses is the standard error in terms of the last digits, as derived from the variance-covariance matrix. Table V. Bond Distances in Ba,S, 0 0 1797 (8)
0
‘I2
Atoms Distance, A Atoms Distance, A Ba(l)-laS(l) 3.24 (4)b Ba(2)-1S(1) 3.27 (4) 2S(1) 3.14 (1) 2S(1) 3.15 (1) 2S(2) 3.21 (7) 2S(2) 3.11 ( 9 ) 4S(2) 3.42 (3) 4S(2) 3.91 (5) S(2)-S(2) 2.32 (9) S(I)-S(2) 3.98 (5) a The number to the left of the S atom shows the number of bonds from the Ba ion. The number in parentheses is the standard deviation.
-b
0
Table VI. Bond Distances in BaS Atoms
Distance, A
Atoms
Distance, A
Ba-4S(1) 4S(2) 4S(2)
3.541 (1) 3.204 (7) 3.344 (7)
S(l)-S(2) S(l)-S(2)
3.388 (7) 2.074 (7)
0
columns by sharing the triangular faces ind two types of columns are present; one has its long axis parallel to a and the other parallel to b and they are interconnected by sharing corners. Ba(2) is surrounded by three S and six S2 ions which form an irregular polyhedron. Sulfur exists as the S32- anion in the structure of BaS3. The S-S distance is 2.074 A, and the S(2)-S(l)-S(2) angle is 114.8 (5)’. The S3 ions form columns and the closest distance between sulfur atoms of adjacent columns is 3.388 A. Barium is surrounded by eight S(2) atoms at the corners of a slightly distorted cube; Le., if the z parameter of S(2) were 1/2, it would be a perfect cube. The Ba-S(2) distances differ, therefore, and are 3.20 and 3.34 A. Four additional S(l) atoms are at 3.54 A SO that Ba can be considered to have 12-fold coordination. Miller and King1 indexed their powder patterns on the basis of an orthorhombic unit cell in which their a aqd b axes _arerelated to our tetragonal a axis by the relation at + bt = bo and ct = 1/2a0. They deduced the presence of the S3 ion in the structure with S-S = 2.15 A and the S-S-S angle as 163’. The S-S distance of 2.32 A in the ,522- ion is considerabl longer than the usual values of 2.0-2.15 A3-5 although a 2.39length is reported for the dithionate ion in Na2S204. However, the large error in our bond length, 0.09 A, does not permit us to say that this value differs significantly from those previously reported. The S-S length of 2.074 A in the S32ion agrees with previously reported values although the angle of 115’ is significantly larger than the values of about 103’ reported in the literature. However, the literature values are for angles in polysulfide ions other than free S32-, or, in the case of (CF3)2S3 and similar molecules, the sulfur atoms are bonded to additional groups which probably affect the S-S-S angle. The Ba2S3 phase apparently forms only at elevated pressure but Bas3 was initially formed by Miller and King in evacuated ampoules and we have reproduced their results as well as recovered it from high-pressure runs. We have calculated the volume available er sulfur atom by subtracting the volume of Ba2+ (r = 1.35 ) from the unit cell volumes of Bas, Ba2S3, and Bas3 and get 54.84, 42.78, and 29.37 A3, respectively. Thus at high pressure the formation
K
w
P
Figure 2. Projection of the structure of Bas, on (001). The symbology of Figure 1 applies here also. Bonds outlining one S , unit are shown.
of polysulfide anions is favored because more of the available volume is utilized by the sulfur atoms. The percentage change in volume AV/V;eactants for the reactions Bas 1/2S 1/2Ba2S3 and Ba2S3 3s 2BaS3 is -4.56% and -13.04%, respectively, and is in accordance with expectations for the formation of compounds found at higher pressures. Acknowledgment. Financial support for this research effort by the Robert A. Welch Foundation, Houston, Tex., and the National Science Foundation (Grant No. G H 36304) is gratefully acknowledged. S. Y. expresses his thanks to the Science and Technology Agency of Japan for support during his visit at this laboratory.
+
+
-+
-+
Registry No. BazS3, 531 11-28-7; BaS3, 12231-01-5. Supplementary Material Available. Tables 11 and 111, listings of structure factor amplitudes for Ba2S3 and BaS3, will appear following these pages in the microfilm edition of this volume of the journal. Photocopies of the supplementary material from this paper only or microfiche (105 X 148 mm, 24X reduction, negatives) containing all of the supplementary material for the papers in this issue may be obtained from the Journals Department, American Chemical Society, 1155 16th St., N.W., Washington, D. C. 20036. Remit check or money order for $3.00 for photocopy or $2.00 for microfiche, referring to code number AIC40475D.
References and Notes (1) W. S. Miller and A. J. King, Z . Kristallogr., Kristallgeometrie, Kristallphys., Kristallchem., 94, 441 (1936). (2) “InternationalTables for X-Ray Crystallography,” Vol. 3, Kynoch Press, Birmingham, England, 1962. (3) F. A. Cotton and G. Wilkinson, “Advanced Inorganic Chemistry,” 3rd ed, Interscience, New York, N. Y., 1972. (4) “Tables of Interatomic Distances and Configuration of Molecules and Ions,” The Chemical Society, London, 1958. (5) R. W. G. Wyckoff, “Crystal Structures,”Vol. I, Interscience, New York, N. Y., 1963.
